7-(Akenylamino)triazolopyrimidines, method for the production thereof and use thereof in controlling harmful fungi and substances containing said triazolopyrimidines

ABSTRACT

7-(Alkenylamino)triazolopyrimidines of the formula I  
                 
wherein the substituents have the following meanings: 
     L is halogen, alkyl, haloalkyl, alkoxy, amino, NHR or NR 2 ; R is alkyl or alkyl-carbonyl; m is 1, 2, 3, 4 or 5; X is halogen, cyano, alkyl, haloalkyl or alkoxy;    R 1  is alkyl or haloalkyl;    R 2  is hydrogen, alkyl or haloalkyl;    R 3  is alkenyl, which can be unsubstituted or partially or completely halogenated or can be substituted according to the Description;    R 4  is hydrogen or alkyl, 
       R 3  and R 4  can also, together with the nitrogen atom to which they are bonded, form a five- or six-membered unsaturated ring which can be interrupted by an atom from the group consisting of O, N and S and/or can carry one or more sub-stituents. Processes for the preparation of these compounds, preparations comprising them and their use in the control of harmful phytopathogenic fungi.

The present invention relates to 7-(alkenylamino)triazolopyrimidines ofthe formula I

in which the substituents have the following meanings:

-   L is, independently of one another, halogen, C₁-C₆-alkyl,    C₁-C₆-haloalkyl, C₁-C₆-alkoxy, amino, NHR or NR₂,    -   R is C₁-C₈-alkyl or C₁-C₈-alkylcarbonyl;-   m is 1, 2, 3, 4 or 5;-   X is halogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄-alkoxy;-   R¹ is C₁-C₃-alkyl or C₁-C₃-haloalkyl;-   R² is hydrogen, C₁-C₃-alkyl or C₁-C₃-haloalkyl;-   R³ is C₂-C₁₀-alkenyl, which can be unsubstituted or partially or    completely halogenated or can carry one to three R^(a) groups:    -   R^(a) is halogen, cyano, nitro, hydroxyl, C₁-C₆-alkylcarbonyl,        C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,        C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylthio, C₁-C₆-alkylamino,        di(C₁-C₆-alkyl)amino, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy,        C₃-C₆-alkynyloxy or C₃-C₆-cycloalkyl,    -   these aliphatic or alicyclic groups for their part being able to        be partially or completely halogenated or to carry one to three        Rb groups:    -   R^(b) is halogen, cyano, nitro, hydroxyl, mercapto, amino,        carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl,        alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio,        alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl,        alkylsulfinyl, alkoxycarbonyl, alkylcarbonyloxy,        alkylaminocarbonyl, dialkylaminocarbonyl,        alkyl-aminothiocarbonyl or dialkylaminothio-carbonyl, the alkyl        groups in these radicals comprising 1 to 6 carbon atoms and the        abovementioned alkenyl or alkynyl groups in these radicals        comprising 2 to 8 carbon atoms;-   R⁴ is hydrogen or C₁-C₂-alkyl,    -   R³ and R⁴ can also, together with the nitrogen atom to which        they are bonded, form a five- or six-membered unsaturated ring        which can carry one or more R^(a) substituents.

In addition, the invention relates to processes for the preparation ofthese compounds, preparations comprising them and their use in thecontrol of harmful phytopathogenic fungi.

6-Phenyl-7-aminotriazolopyrimidines are generally known from EP-A 71 792and EP-A 550 113. The compounds disclosed in the abovementioneddocuments are known for the control of harmful fungi.

However, in many cases, their action is unsatisfactory.

It is an object of the present invention to provide compounds which havean improved action and/or a broadened spectrum of activity.

We have found that this object is achieved by the compounds defined atthe start. Furthermore, processes for and intermediates in theirpreparation, preparations comprising them and methods for the control ofharmful fungi with the use of the compounds I have been found.

The compounds of the formula I are distinguished from those from theabovementioned documents by the form of the alkenyl group in the7-position of the triazolopyrimidine skeleton, which exhibits branchingat the α-carbon atom.

The compounds of the formula I have, in comparison with the knowncompounds, an increased effectiveness against harmful fungi.

The compounds according to the invention can be obtained in variousways. They are advantageously obtained by reaction ofdihalotriazolopyrimidines of the formula II, in which Hal is a halogenatom, such as bromine or, in particular, chlorine, with amines of theformula III under conditions generally known from WO 98/46608.

The reaction of II with amines III is advantageously carried out at 0°C. to 70° C., preferably 10° C. to 35° C., preferably in the presence ofan inert solvent, such as ethers, e.g. dioxane, diethyl ether or, inparticular, tetrahydrofuran, halogenated hydrocarbons, such asdichloromethane, and aromatic hydrocarbons, such as, for example,toluene.

The use of a base, such as tertiary amines, for example triethylamine,or inorganic bases, such as potassium carbonate, is preferred; excessamine of the formula III can also act as base.

Amines of the formula III are known in some cases or can be preparedaccording to known methods, for example from the corresponding alcoholsvia the tosylates and phthalimides [cf. J. Am. Chem. Soc., Vol. 117, p.7025 (1995); WO 93/20804], by reduction of the corresponding nitriles[cf. Heterocycles, Vol. 35, p. 2 (1993); Synthetic Commun., Vol. 25, p.413 (1995); Tetrahedron Lett., p. 2933 (1995)] or reductive amination ofketones [cf. J. Am. Chem. Soc., Vol. 122, p. 9556 (2000); Org. Lett., p.731 (2001); J. Med. Chem., p. 1566 (1988)], from the correspondinghalides [cf. Synthesis, p. 150 (1995)] and if necessary from subsequentalkylation. The CR¹R² group can optionally be formed by a Grignardreaction with corresponding nitriles or carboxylic acid anhydrides [cf.J. Org. Chem., p. 5056 (1992)]. Amines of the formula III are alsoaccessible by the route known from WO 02/088125.

Compounds of the formula I in which X is halogen (formula I.A), in partlar chlorine, are a preferred object of the invention.

Compounds of the formula I in which X represents cyano or C₁-C₆-alkoxy(formula I.B) can advantageously be prepared from compounds I in which Xrepresents halogen [Hal], preferably chlorine, which correspond toformula I.A.

Compounds I.A are reacted with compounds M-X′ (formula IV) to givecompound I.B. Compounds IV represent, depending on the meaning of the X′group to be introduced, an inorganic cyanide or an alkoxide. Thereaction is advantageously carried out in the presence of an inertsolvent. The cation M in the formula IV has little meaning; forpractical reasons, ammonium, tetraalkylammonium, alkali metal oralkaline earth metal salts are usually preferred.

The reaction temperature is usually from 0 to 120° C., preferably from10 to 40° C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].

Suitable solvents include ethers, such as dioxane, diethyl ether and,preferably, tetrahydrofuran, halogenated hydrocarbons, such asdichloromethane, and aromatic hydrocarbons, such as toluene.

Compounds I in which X is C₁-C₄-alkyl (formula I.C) can advantageouslybe prepared by the routes outlined below starting from startingmaterials of the formula I.A.

Compounds of the formula I.C in which X″ represents C₁-C₄-alkyl can beobtained by coupling 5-halotriazolopyrimidines of the formula I.A withorganometallic reagents of the formula V. In one embodiment of thisprocess, the reaction is carried out under transition metal catalysis,such as Ni or Pd catalysis.

In formula V, X″ is C₁-C₄-alkyl and M is a metal ion with the valency y,such as, for example, B, Zn or Sn. This reaction can, for example, becarried out analogously to the following methods: J. Chem. Soc. PerkinTrans., 1, 1187 (1994), ibid., 1, 2345 (1996); WO 99/41255; Aust. J.Chem., Vol. 43, p. 733 (1990); J. Org. Chem., Vol. 43, p. 358 (1978); J.Chem. Soc. Chem. Commun., p. 866 (1979); Tetrahedron Lett., Vol. 34, p.8267 (1993); ibid., Vol. 33, p. 413 (1992).

Compounds of the formula I in which X is C₁-C₄-alkyl or C₁-C₄-haloalkyl(formula I.C) can advantageously also be obtained by the followingsynthetic route:

The 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines Vil are obtainedstarting from 5-aminotriazole VI and the ketoester VII. In formula VII,R is a C₁-C₄-alkyl group, in particular methyl or ethyl. The5-methyl-7-hydroxy-6-phenyltriazolopyrimidines are obtained by use ofthe readily accessible 2-phenylacetoacetic acid esters VIIa with X″═CH₃[cf. Chem. Pharm. Bull., 9, 801 (1961)]. 5-Aminotriazole VI iscommercially available. The starting compounds VII are advantageouslyprepared under the conditions known from EP-A 1 002 788.

The 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines VII thus obtained arereacted with halogenating agents [HAL] to give 7-halotriazolopyrimidinesof the formula IX.

Chlorinating or brominating agents, such as phosphoryl bromide,phosphoryl chloride, thionyl chloride, thionyl bromide or sulfurylchloride, are preferably used. The reaction can be carried out neat orin the presence of a solvent. Normal reaction temperatures are from 0 to150° C. or, preferably, from 80 to 125° C.

The reaction of 1× with amines III is advantageously carried out at 0°C. to 70° C., preferably 10° C. to 35° C., preferably in the presence ofan inert solvent, such as ethers, e.g. dioxane, diethyl ether or, inparticular, tetrahydrofuran, halogenated hydrocarbons, such asdichloromethane, and aromatic hydrocarbons, such as, for example,toluene [cf. WO 98/46608].

The use of a base, such as tertiary amines, for example triethylamine,or inorganic bases, such as potassium carbonate, is preferred; excessamine of the formula III can also act as base.

Compounds of the formula I.C can alternatively also be prepared fromcompounds I.A and malonates of the formula XI. In formula XI, X′″represents hydrogen, C₁-C₃-alkyl or C₁-C₃-haloalkyl and R representsC₁-C₄-alkyl. They are reacted to give compounds of the formula XII anddecarboxylated to give compounds I.C [cf. U.S. Pat. No. 5,994,360].

The malonates XI are known in the literature [J. Am. Chem. Soc., Vol.64, 2714 (1942); J. Org. Chem., Vol. 39, 2172 (1974); Helv. Chim. Acta,Vol. 61, 1565 (1978)] or can be prepared according to the citedliterature.

The subsequent saponification of the ester XII is carried out undergenerally conventional conditions; the basic or the acidicsaponification of the compounds XII may be advantageous, depending onthe various structural elements. Under the conditions of the estersaponification, the decarboxylation to give I.C may already becompletely or partially carried out.

The decarboxylation is usually carried out at temperatures of 20° C. to180° C., preferably 50° C. to 120° C., in an inert solvent, optionallyin the presence of an acid.

Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid,formic acid, acetic acid or p-toluenesulfonic acid. Suitable solventsare water, aliphatic hydrocarbons, such as pentane, hexane, cyclohexaneand petroleum ether, aromatic hydrocarbons, such as toluene or o-, m-and p-xylene, halogenated hydrocarbons, such as methylene chloride,chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropylether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran,nitriles, such as acetonitrile and propionitrile, ketones, such asacetone, methyl ethyl ketone, diethyl ketone and tert-butyl methylketone, alcohols, such as methanol, ethanol, n-propanol, isopropanol,n-butanol and tert-butanol, and dimethyl sulfoxide, dimethylformamideand dimethylacetamide; the reaction is particularly preferably carriedout in hydrochloric acid or acetic acid. Mixtures of the abovementionedsolvents can also be used.

The reaction mixtures are worked up conventionally, e.g. by mixing withwater, separating the phases and possibly chromatographic purificationof the crude products. Some of the intermediates and final products areobtained in the form of colorless or slightly brownish viscous oilswhich, under reduced pressure and at moderately elevated temperature,are freed from or purified of volatile constituents. Provided that theintermediates and final products are obtained as solids, thepurification can also take place by recrystallization or trituration.

If individual compounds I are not accessible by the routes describedabove, they can be prepared by derivatization of other compounds I.

If mixtures of isomers are obtained in the synthesis, a separation isgenerally not absolutely essential, however, since the individualisomers can sometimes be converted into one another during the workupfor the application or in the application (e.g. under the action oflight, acid or bases). Appropriate conversions can also take place afterthe application, for example, with the treatment of plants, in thetreated plants or in the harmful fungi to be controlled.

Collective terms were used in the definitions of the symbols given inthe above formulae, which collective terms are generally representativeof the following substituents:

halogen: fluorine, chlorine, bromine and iodine;

alkyl: saturated, straight-chain or branched hydrocarbon radicals with 1to 4, 6 or 8 carbon atoms, e.g. C₁-C₆-alkyl, such as methyl, ethyl,propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl,1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl,1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; haloalkyl:straight-chain or branched alkyl groups with 1 to 2, 4 or 6 carbon atoms(as mentioned above), in which the hydrogen atoms in these groups can bepartially or completely replaced by halogen atoms as mentioned above, inparticular C₁-C₂-haloalkyl, such as chloromethyl, bromomethyl,dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl,chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl,2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or1,1,1-trifluoroprop-2-yl;

alkenyl: unsaturated, straight-chain or branched hydrocarbon radicalswith 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds in anyposition, e.g. C₂-C₆-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl,1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl,1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl,2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl,2-methyl-2-butenyl, 3-methyl-2butenyl, 1-methyl-3-butenyl,2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl,1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl,5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl,3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl,1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl,3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl,1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl,2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and1-ethyl-2-methyl-2-propenyl;

Alkenylene: unsaturated, straight-chain hydrocarbon radicals with 3 or 4carbon atoms and a double bond in any position.

If R¹ and R² are different, the carbon atom carrying the R¹ to R³ groupsrepresents a chiral center. The (R)- and (S)-isomers and the racematesof the compounds of the formula I come within the scope of the presentinvention.

The embodiments of the intermediates which are especially preferred withregard to the variables correspond to those of the radicals L_(m), R¹,R², R³, R⁴ and X of the formula I.

In view of the intended use of the triazolopyrimidines of the formula I,the following meanings of the substituents, in each case alone or incombination, are especially preferred:

Preference is given to compounds I in which R¹ is methyl or halomethyl,such as trifluoromethyl.

An additional preferred object are compounds I in which R² is hydrogen.

Preference is given to compounds I in which R³ is straight-chain orbranched C₂-C₁₀-alkenyl which can be unsubstituted or partially orcompletely halogenated and/or can carry one to three C₁-C₃-alkoxygroups. A particularly preferred object are compounds I in which R³ isstraight-chain or branched C₂-C₁₀-alkenyl which is unsubstituted.

Preference is similarly given to compounds I in which R³ and R⁴ togetherform a C₃-C₄-alkenylene chain which can be substituted by one or twomethyl or halomethyl groups.

Particular preference is given to compounds I in which R⁴ representshydrogen.

Preference is similarly given to compounds I in which R⁴ is methyl orethyl.

Preference is given to compounds I in which at least one L group is inthe ortho position with regard to the point of linkage with thetriazolopyrimidine skeleton; in particular those in which the index mhas the value 1, 2 or 3.

Preference is given to compounds I in which L_(m) represents fluorine,chlorine, methyl, C₁-haloalkyl, methoxy, amino, NHR or NR₂, in which Ris methyl or acetyl.

In addition, particular preference is given to compounds I, wherein thephenyl group substituted by L_(m) is the group A

in which # is the point of linkage with the triazolopyrimidine skeletonand

L¹ represents fluorine, chlorine, CH₃ or CF₃;

L² and L⁴ represent, independently of one another, hydrogen or fluorine;

L³ represents hydrogen, fluorine, chlorine, CH₃, OCH₃, amino, NHR orNR₂; and L⁵ represents hydrogen, chlorine, fluorine or CH₃.

Special preference is given to compounds 1, wherein L_(m) is one of thefollowing substituent combinations: 2-fluoro-6-chloro, 2,6-difluoro,2,6-dichloro, 2-fluoro-6-methyl, 2,4,6-trifluoro,2,6-difluoro-4-methoxy, pentafluoro, 2-methyl-4-fluoro,2-trifluoromethyl, 2-methoxy-6-fluoro, 2-chloro, 2-fluoro, 2,4-difluoro,2-fluoro-4-chloro, 2-chloro-4-fluoro, 2,3-difluoro, 2,5-difluoro,2,3,4-trifluoro, 2-methyl, 2,4-dimethyl, 2-methyl-4-chloro,2-fluoro-4-methyl, 2,6-dimethyl, 2,4,6-trimethyl, 2,6-difluoro-4-methyl,2-trifluoromethyl-4-fluoro, 2-trifluoromethyl-5-fluoro or2-trifluoromethyl-5-chloro.

Special preference is given to compounds I in which X represents halogenor C₁-C₄-alkyl, such as chlorine or methyl, in particular chlorine.

Particular preference is given, in view of their use, to the compounds Icompiled in the following tables. The groups mentioned in the tables fora substituent additionally represent, considered per se, independentlyof the combination in which they are mentioned, a particularly preferredform of the substituent in question.

Table 1

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-fluoro-6-chloro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A Table 2 Compounds of the formula I in which Xrepresents chlorine, L_(m) represents 2,6-difluoro and R² representshydrogen and the combination of R¹, R³ and R⁴ for a compound correspondsin each case to a row of table A

Table 3

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,6-dichloro and R² represents hydrogen and the combinationof R¹, R³ and R⁴ for a compound corresponds in each case to a row oftable A

Table 4

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-fluoro-6-methyl and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 5

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,4,6-trifluoro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 6

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,6-difluoro-4-methoxy and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 7

Compounds of the formula I in which X represents chlorine, L_(m)represents pentafluoro and R² represents hydrogen and the combination ofR¹, R³ and R⁴ for a compound corresponds in each case to a row of tableA

Table 8

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-methyl-4-fluoro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 9

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-trifluoromethyl and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 10

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-methoxy-6-fluoro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 11

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-chloro and R² represents hydrogen and the combination ofR¹, R³ and R⁴ for a compound corresponds in each case to a row of tableA

Table 12

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-fluoro and R² represents hydrogen and the combination ofR¹, R³ and R⁴ for a compound corresponds in each case to a row of tableA

Table 13

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,4-difluoro and R² represents hydrogen and the combinationof R¹, R³ and R⁴ for a compound corresponds in each case to a row oftable A

Table 14

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-fluoro-4-chloro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 15

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-chloro-4-fluoro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 16

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,3-difluoro and R² represents hydrogen and the combinationof R¹, R³ and R⁴ for a compound corresponds in each case to a row oftable A

Table 17

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,5-difluoro and R² represents hydrogen and the combinationof R¹, R³ and R⁴ for a compound corresponds in each case to a row oftable A

Table 18

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,3,4-trifluoro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 19

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-methyl and R² represents hydrogen and the combination ofR¹, R³ and R⁴ for a compound corresponds in each case to a row of tableA

Table 20

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,4-dimethyl and R² represents hydrogen and the combinationof R¹, R³ and R⁴ for a compound corresponds in each case to a row oftable A

Table 21

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-methyl-4-chloro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 22

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-fluoro-4-methyl and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 23

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,6-dimethyl and R² represents hydrogen and the combinationof R¹, R³ and R⁴ for a compound corresponds in each case to a row oftable A

Table 24

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,4,6-trimethyl and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 25

Compounds of the formula I in which X represents chlorine, L_(m)represents 2,6-difluoro-4-methyl and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 26

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-trifluoromethyl-4-fluoro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 27

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-trifluoromethyl-5-fluoro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A

Table 28

Compounds of the formula I in which X represents chlorine, L_(m)represents 2-trifluoromethyl-5-chloro and R² represents hydrogen and thecombination of R¹, R³ and R⁴ for a compound corresponds in each case toa row of table A TABLE A No. R¹ R³ R⁴ A-1 CH₃ CH═CH₂ H A-2 CH₃ CH═CH₂CH₃ A-3 CH₃ CH═CH₂ CH₂CH₃ A-4 CH₃ C(CH₃)═CH₂ H A-5 CH₃ C(CH₃)═CH₂ CH₃A-6 CH₃ C(CH₃)═CH₂ CH₂CH₃ A-7 CH₃ CH═CHCH₃ H A-8 CH₃ CH═CHCH₃ CH₃ A-9CH₃ CH═CHCH₃ CH₂CH₃ A-10 CH₃ CH═CHCH₂CH₃ H A-11 CH₃ CH═CHCH₂CH₃ CH₃ A-12CH₃ CH═CHCH₂CH₃ CH₂CH₃ A-13 CH₃ CH═C(CH₃)₂ H A-14 CH₃ CH═C(CH₃)₂ CH₃A-15 CH₃ CH═C(CH₃)₂ CH₂CH₃ A-16 CH₃ C(CH₃)═CHCH₃ H A-17 CH₃ C(CH₃)═CHCH₃CH₃ A-18 CH₃ C(CH₃)═CHCH₃ CH₂CH₃ A-19 CH₃ C(CH₂CH₃)═CH₂ H A-20 CH₃C(CH₂CH₃)═CH₂ CH₃ A-21 CH₃ C(CH₂CH₃)═CH₂ CH₂CH₃ A-22 CH₃ CH═CH(CH₂)₂CH₃H A-23 CH₃ CH═CH(CH₂)₂CH₃ CH₃ A-24 CH₃ CH═CH(CH₂)₂CH₃ CH₂CH₃ A-25 CH₃CH═CHCH(CH₃)₂ H A-26 CH₃ CH═CHCH(CH₃)₂ CH₃ A-27 CH₃ CH═CHCH(CH₃)₂ CH₂CH₃A-28 CH₃ CH═C(CH₃)CH₂CH₃ H A-29 CH₃ CH═C(CH₃)CH₂CH₃ CH₃ A-30 CH₃CH═C(CH₃)CH₂CH₃ CH₂CH₃ A-31 CH₃ C(CH₃)═CHCH₂CH₃ H A-32 CH₃C(CH₃)═CHCH₂CH₃ CH₃ A-33 CH₃ C(CH₃)═CHCH₂CH₃ CH₂CH₃ A-34 CH₃C(CH₃)═C(CH₃)₂ H A-35 CH₃ C(CH₃)═C(CH₃)₂ CH₃ A-36 CH₃ C(CH₃)═C(CH₃)₂CH₂CH₃ A-37 CH₃ C(═CH₂)CH(CH₃)₂ H A-38 CH₃ C(═CH₂)CH(CH₃)₂ CH₃ A-39 CH₃C(═CH₂)CH(CH₃)₂ CH₂CH₃ A-40 CH₃ C(CH₂CH₃)═CHCH₃ H A-41 CH₃C(CH₂CH₃)═CHCH₃ CH₃ A-42 CH₃ C(CH₂CH₃)═CHCH₃ CH₂CH₃ A-43 CH₃C(═CH₂)CH₂CH₂CH₃ H A-44 CH₃ C(═CH₂)CH₂CH₂CH₃ CH₃ A-45 CH₃C(═CH₂)CH₂CH₂CH₃ CH₂CH₃ A-46 CH₃ CH₂CH═CH₂ H A-47 CH₃ CH₂CH═CH₂ CH₃ A-48CH₃ CH₂CH═CH₂ CH₂CH₃ A-49 CH₃ CH₂C(CH₃)═CH₂ H A-50 CH₃ CH₂C(CH₃)═CH₂ CH₃A-51 CH₃ CH₂C(CH₃)═CH₂ CH₂CH₃ A-52 CH₃ CH₂CH═CHCH₃ H A-53 CH₃CH₂CH═CHCH₃ CH₃ A-54 CH₃ CH₂CH═CHCH₃ CH₂CH₃ A-55 CH₃ CH(CH₃)CH═CH₂ HA-56 CH₃ CH(CH₃)CH═CH₂ CH₃ A-57 CH₃ CH(CH₃)CH═CH₂ CH₂CH₃ A-58 CH₃CH₂CH═C(CH₃)₂ H A-59 CH₃ CH₂CH═C(CH₃)₂ CH₃ A-60 CH₃ CH₂CH═C(CH₃)₂ CH₂CH₃A-61 CH₃ CH₂C(CH₃)═CHCH₃ H A-62 CH₃ CH₂C(CH₃)═CHCH₃ CH₃ A-63 CH₃CH₂C(CH₃)═CHCH₃ CH₂CH₃ A-64 CH₃ CH₂CH₂CH═CH₂ H A-65 CH₃ CH₂CH₂CH═CH₂ CH₃A-66 CH₃ CH₂CH₂CH═CH₂ CH₂CH₃ A-67 CH₃ CH₂CH₂CH═CHCH₃ H A-68 CH₃CH₂CH₂CH═CHCH₃ CH₃ A-69 CH₃ CH₂CH₂CH═CHCH₃ CH₂CH₃ A-70 CH₃CH₂CH₂CH═C(CH₃)₂ H A-71 CH₃ CH₂CH₂CH═C(CH₃)₂ CH₃ A-72 CH₃CH₂CH₂CH═C(CH₃)₂ CH₂CH₃ A-73 CH₃ CH₂CH₂CH₂CH═CH₂ H A-74 CH₃CH₂CH₂CH₂CH═CH₂ CH₃ A-75 CH₃ CH₂CH₂CH₂CH═CH₂ CH₂CH₃ A-76 CH₃CH₂CH₂CH₂CH═CHCH₃ H A-77 CH₃ CH₂CH₂CH₂CH═CHCH₃ CH₃ A-78 CH₃CH₂CH₂CH₂CH═CHCH₃ CH₂CH₃ A-79 CH₃ CH₂CH₂CH₂CH═C(CH₃)₂ H A-80 CH₃CH₂CH₂CH₂CH═C(CH₃)₂ CH₃ A-81 CH₃ CH₂CH₂CH₂CH═C(CH₃)₂ CH₂CH₃ A-82 CH₃(CH₂)₄CH═CH₂ H A-83 CH₃ (CH₂)₄CH═CH₂ CH₃ A-84 CH₃ (CH₂)₄CH═CH₂ CH₂CH₃A-85 CH₃ —CH₂CH═CHCH₂-# A-86 CH₃ —CH═CHCH₂CH₂-# A-87 CH₃—CH═CHCH₂CH(CH₃)-# A-88 CH₃ —CH═CHCH₂-# A-89 CH₃ —CH═CHCH(CH₃)-# A-90CF₃ CH═CH₂ H A-91 CF₃ CH═CH₂ CH₃ A-92 CF₃ CH═CH₂ CH₂CH₃ A-93 CF₃C(CH₃)═CH₂ H A-94 CF₃ C(CH₃)═CH₂ CH₃ A-95 CF₃ C(CH₃)═CH₂ CH₂CH₃ A-96 CF₃CH═CHCH₃ H A-97 CF₃ CH═CHCH₃ CH₃ A-98 CF₃ CH═CHCH₃ CH₂CH₃ A-99 CF₃CH═CHCH₂CH₃ H A-100 CF₃ CH═CHCH₂CH₃ CH₃ A-101 CF₃ CH═CHCH₂CH₃ CH₂CH₃A-102 CF₃ CH═C(CH₃)₂ H A-103 CF₃ CH═C(CH₃)₂ CH₃ A-104 CF₃ CH═C(CH₃)₂CH₂CH₃ A-105 CF₃ C(CH₃)═CHCH₃ H A-106 CF₃ C(CH₃)═CHCH₃ CH₃ A-107 CF₃C(CH₃)═CHCH₃ CH₂CH₃ A-108 CF₃ C(CH₂CH₃)═CH₂ H A-109 CF₃ C(CH₂CH₃)═CH₂CH₃ A-110 CF₃ C(CH₂CH₃)═CH₂ CH₂CH₃ A-111 CF₃ CH═CH(CH₂)₂CH₃ H A-112 CF₃CH═CH(CH₂)₂CH₃ CH₃ A-113 CF₃ CH═CH(CH₂)₂CH₃ CH₂CH₃ A-114 CF₃CH═CHCH(CH₃)₂ H A-115 CF₃ CH═CHCH(CH₃)₂ CH₃ A-116 CF₃ CH═CHCH(CH₃)₂CH₂CH₃ A-117 CF₃ CH═C(CH₃)CH₂CH₃ H A-118 CF₃ CH═C(CH₃)CH₂CH₃ CH₃ A-119CF₃ CH═C(CH₃)CH₂CH₃ CH₂CH₃ A-120 CF₃ C(CH₃)═CHCH₂CH₃ H A-121 CF₃C(CH₃)═CHCH₂CH₃ CH₃ A-122 CF₃ C(CH₃)═CHCH₂CH₃ CH₂CH₃ A-123 CF₃C(CH₃)═C(CH₃)₂ H A-124 CF₃ C(CH₃)═C(CH₃)₂ CH₃ A-125 CF₃ C(CH₃)═C(CH₃)₂CH₂CH₃ A-126 CF₃ C(═CH₂)CH(CH₃)₂ H A-127 CF₃ C(═CH₂)CH(CH₃)₂ CH₃ A-128CF₃ C(═CH₂)CH(CH₃)₂ CH₂CH₃ A-129 CF₃ C(CH₂CH₃)═CHCH₃ H A-130 CF₃C(CH₂CH₃)═CHCH₃ CH₃ A-131 CF₃ C(CH₂CH₃)═CHCH₃ CH₂CH₃ A-132 CF₃C(═CH₂)CH₂CH₂CH₃ H A-133 CF₃ C(═CH₂)CH₂CH₂CH₃ CH₃ A-134 CF₃C(═CH₂)CH₂CH₂CH₃ CH₂CH₃ A-135 CF₃ CH₂CH═CH₂ H A-136 CF₃ CH₂CH═CH₂ CH₃A-137 CF₃ CH₂CH═CH₂ CH₂CH₃ A-138 CF₃ CH₂C(CH₃)═CH₂ H A-139 CF₃CH₂C(CH₃)═CH₂ CH₃ A-140 CF₃ CH₂C(CH₃)═CH₂ CH₂CH₃ A-141 CF₃ CH₂CH═CHCH₃ HA-142 CF₃ CH₂CH═CHCH₃ CH₃ A-143 CF₃ CH₂CH═CHCH₃ CH₂CH₃ A-144 CF₃CH(CH₃)CH═CH₂ H A-145 CF₃ CH(CH₃)CH═CH₂ CH₃ A-146 CF₃ CH(CH₃)CH═CH₂CH₂CH₃ A-147 CF₃ CH₂CH═C(CH₃)₂ H A-148 CF₃ CH₂CH═C(CH₃)₂ CH₃ A-149 CF₃CH₂CH═C(CH₃)₂ CH₂CH₃ A-150 CF₃ CH₂C(CH₃)═CHCH₃ H A-151 CF₃CH₂C(CH₃)═CHCH₃ CH₃ A-152 CF₃ CH₂C(CH₃)═CHCH₃ CH₂CH₃ A-153 CF₃CH₂CH₂CH═CH₂ H A-154 CF₃ CH₂CH₂CH═CH₂ CH₃ A-155 CF₃ CH₂CH₂CH═CH₂ CH₂CH₃A-156 CF₃ CH₂CH₂CH═CHCH₃ H A-157 CF₃ CH₂CH₂CH═CHCH₃ CH₃ A-158 CF₃CH₂CH₂CH═CHCH₃ CH₂CH₃ A-159 CF₃ CH₂CH₂CH═C(CH₃)₂ H A-160 CF₃CH₂CH₂CH═C(CH₃)₂ CH₃ A-161 CF₃ CH₂CH₂CH═C(CH₃)₂ CH₂CH₃ A-162 CF₃CH₂CH₂CH₂CH═CH₂ H A-163 CF₃ CH₂CH₂CH₂CH═CH₂ CH₃ A-164 CF₃CH₂CH₂CH₂CH═CH₂ CH₂CH₃ A-165 CF₃ CH₂CH₂CH₂CH═CHCH₃ H A-166 CF₃CH₂CH₂CH₂CH═CHCH₃ CH₃ A-167 CF₃ CH₂CH₂CH₂CH═CHCH₃ CH₂CH₃ A-168 CF₃CH₂CH₂CH₂CH═C(CH₃)₂ H A-169 CF₃ CH₂CH₂CH₂CH═C(CH₃)₂ CH₃ A-170 CF₃CH₂CH₂CH₂CH═C(CH₃)₂ CH₂CH₃ A-171 CF₃ (CH₂)₄CH═CH₂ H A-172 CF₃(CH₂)₄CH═CH₂ CH₃ A-173 CF₃ (CH₂)₄CH═CH₂ CH₂CH₃ A-174 CF₃ —CH₂CH═CHCH₂-#A-175 CF₃ —CH═CHCH₂CH₂-# A-176 CF₃ —CH═CHCH₂CH(CH₃)-# A-177 CF₃—CH═CHCH₂-# A-178 CF₃ —CH═CHCH(CH₃)-# A-179 CH₂F CH═CH₂ H A-180 CH₂FCH═CH₂ CH₃ A-181 CH₂F CH═CH₂ CH₂CH₃ A-182 CH₂F C(CH₃)═CH₂ H A-183 CH₂FC(CH₃)═CH₂ CH₃ A-184 CH₂F C(CH₃)═CH₂ CH₂CH₃ A-185 CH₂F CH═CHCH₃ H A-186CH₂F CH═CHCH₃ CH₃ A-187 CH₂F CH═CHCH₃ CH₂CH₃ A-188 CH₂F CH═CHCH₂CH₃ HA-189 CH₂F CH═CHCH₂CH₃ CH₃ A-190 CH₂F CH═CHCH₂CH₃ CH₂CH₃ A-191 CH₂FCH═C(CH₃)₂ H A-192 CH₂F CH═C(CH₃)₂ CH₃ A-193 CH₂F CH═C(CH₃)₂ CH₂CH₃A-194 CH₂F C(CH₃)═CHCH₃ H A-195 CH₂F C(CH₃)═CHCH₃ CH₃ A-196 CH₂FC(CH₃)═CHCH₃ CH₂CH₃ A-197 CH₂F C(CH₂CH₃)═CH₂ H A-198 CH₂F C(CH₂CH₃)═CH₂CH₃ A-199 CH₂F C(CH₂CH₃)═CH₂ CH₂CH₃ A-200 CH₂F CH═CH(CH₂)₂CH₃ H A-201CH₂F CH═CH(CH₂)₂CH₃ CH₃ A-202 CH₂F CH═CH(CH₂)₂CH₃ CH₂CH₃ A-203 CH₂FCH═CHCH(CH₃)₂ H A-204 CH₂F CH═CHCH(CH₃)₂ CH₃ A-205 CH₂F CH═CHCH(CH₃)₂CH₂CH₃ A-206 CH₂F CH═C(CH₃)CH₂CH₃ H A-207 CH₂F CH═C(CH₃)CH₂CH₃ CH₃ A-208CH₂F CH═C(CH₃)CH₂CH₃ CH₂CH₃ A-209 CH₂F C(CH₃)═CHCH₂CH₃ H A-210 CH₂FC(CH₃)═CHCH₂CH₃ CH₃ A-211 CH₂F C(CH₃)═CHCH₂CH₃ CH₂CH₃ A-212 CH₂FC(CH₃)═C(CH₃)₂ H A-213 CH₂F C(CH₃)═C(CH₃)₂ CH₃ A-214 CH₂F C(CH₃)═C(CH₃)₂CH₂CH₃ A-215 CH₂F C(═CH₂)CH(CH₃)₂ H A-216 CH₂F C(═CH₂)CH(CH₃)₂ CH₃ A-217CH₂F C(═CH₂)CH(CH₃)₂ CH₂CH₃ A-218 CH₂F C(CH₂CH₃)═CHCH₃ H A-219 CH₂FC(CH₂CH₃)═CHCH₃ CH₃ A-220 CH₂F C(CH₂CH₃)═CHCH₃ CH₂CH₃ A-221 CH₂FC(═CH₂)CH₂CH₂CH₃ H A-222 CH₂F C(═CH₂)CH₂CH₂CH₃ CH₃ A-223 CH₂FC(═CH₂)CH₂CH₂CH₃ CH₂CH₃ A-224 CH₂F CH₂CH═CH₂ H A-225 CH₂F CH₂CH═CH₂ CH₃A-226 CH₂F CH₂CH═CH₂ CH₂CH₃ A-227 CH₂F CH₂C(CH₃)═CH₂ H A-228 CH₂FCH₂C(CH₃)═CH₂ CH₃ A-229 CH₂F CH₂C(CH₃)═CH₂ CH₂CH₃ A-230 CH₂F CH₂CH═CHCH₃H A-231 CH₂F CH₂CH═CHCH₃ CH₃ A-232 CH₂F CH₂CH═CHCH₃ CH₂CH₃ A-233 CH₂FCH(CH₃)CH═CH₂ H A-234 CH₂F CH(CH₃)CH═CH₂ CH₃ A-235 CH₂F CH(CH₃)CH═CH₂CH₂CH₃ A-236 CH₂F CH₂CH═C(CH₃)₂ H A-237 CH₂F CH₂CH═C(CH₃)₂ CH₃ A-238CH₂F CH₂CH═C(CH₃)₂ CH₂CH₃ A-239 CH₂F CH₂C(CH₃)═CHCH₃ H A-240 CH₂FCH₂C(CH₃)═CHCH₃ CH₃ A-241 CH₂F CH₂C(CH₃)═CHCH₃ CH₂CH₃ A-242 CH₂FCH₂CH₂CH═CH₂ H A-243 CH₂F CH₂CH₂CH═CH₂ CH₃ A-244 CH₂F CH₂CH₂CH═CH₂CH₂CH₃ A-245 CH₂F CH₂CH₂CH═CHCH₃ H A-246 CH₂F CH₂CH₂CH═CHCH₃ CH₃ A-247CH₂F CH₂CH₂CH═CHCH₃ CH₂CH₃ A-248 CH₂F CH₂CH₂CH═C(CH₃)₂ H A-249 CH₂FCH₂CH₂CH═C(CH₃)₂ CH₃ A-250 CH₂F CH₂CH₂CH═C(CH₃)₂ CH₂CH₃ A-251 CH₂FCH₂CH₂CH₂CH═CH₂ H A-252 CH₂F CH₂CH₂CH₂CH═CH₂ CH₃ A-253 CH₂FCH₂CH₂CH₂CH═CH₂ CH₂CH₃ A-254 CH₂F CH₂CH₂CH₂CH═CHCH₃ H A-255 CH₂FCH₂CH₂CH₂CH═CHCH₃ CH₃ A-256 CH₂F CH₂CH₂CH₂CH═CHCH₃ CH₂CH₃ A-257 CH₂FCH₂CH₂CH₂CH═C(CH₃)₂ H A-258 CH₂F CH₂CH₂CH₂CH═C(CH₃)₂ CH₃ A-259 CH₂FCH₂CH₂CH₂CH═C(CH₃)₂ CH₂CH₃ A-260 CH₂F (CH₂)₄CH═CH₂ H A-261 CH₂F(CH₂)₄CH═CH₂ CH₃ A-262 CH₂F (CH₂)₄CH═CH₂ CH₂CH₃ A-263 CH₂F—CH₂CH═CHCH₂-# A-264 CH₂F —CH═CHCH₂CH₂-# A-265 CH₂F —CH═CHCH₂CH(CH₃)-#A-266 CH₂F —CH═CHCH₂-# A-267 CH₂F —CH═CHCH(CH₃)-##indicates the bond to the nitrogen atom

The compounds I are suitable as fungicides. They are distinguished by anoutstanding effectiveness against a broad spectrum of phytopathogenicfungi, especially from the classes of the Ascomycetes, Deuteromycetes,Oomycetes and Basidiomycetes. Some are systemically effective and theycan be used in plant protection as foliar and soil fungicides.

They are particularly important in the control of a multitude of fungion various cultivated plants, such as wheat, rye, barley, oats, rice,maize, grass, bananas, cotton, soya, coffee, sugar cane, vines, fruitsand ornamental plants, and vegetables, such as cucumbers, beans,tomatoes, potatoes and cucurbits, and on the seeds of these plants.

They are especially suitable for controlling the following plantdiseases:

-   -   Alternaria species on fruit and vegetables,    -   Bipolaris and Drechslera species on cereals, rice and lawns,    -   Blumeria graminis (powdery mildew) on cereals,    -   Botrytis cinerea (gray mold) on strawberries, vegetables,        ornamental plants and grapevines,    -   Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,    -   Fusarium and Verticillium species on various plants,    -   Mycosphaerella species on cereals, bananas and peanuts,    -   Phytophthora infestans on potatoes and tomatoes,    -   Plasmopara viticola on grapevines,    -   Podosphaera leucotricha on apples,    -   Pseudocercosporella herpotrichoides on wheat and barley,    -   Pseudoperonospora species on hops and cucumbers,    -   Puccinia species on cereals,    -   Pyricularia oryzae on rice,    -   Rhizoctonia species on cotton, rice and lawns,    -   Septoria tritici and Stagonospora nodorum on wheat,    -   Uncinula necatoron grapevines,    -   Ustilago species on cereals and sugar cane, and    -   Venturia species (scab) on apples and pears.

The compounds I are also suitable for controlling harmful fungi, such asPaecilomyces variotii, in the protection of materials (e.g. wood, paper,paint dispersions, fibers or fabrics) and in the protection of storedproducts.

The compounds I are employed by treating the fungi or the plants, seeds,materials or soil to be protected from fungal attack with a fungicidallyeffective amount of the active compounds. The application can be carriedout both before and after the infection of the materials, plants orseeds by the fungi.

The fungicidal compositions generally comprise between 0.1 and 95%,preferably between 0.5 and 90%, by weight of active compound.

When employed in plant protection, the amounts applied are, depending onthe kind of effect desired, between 0.01 and 2.0 kg of active compoundper ha.

In seed treatment, amounts of active compound of 0.001 to 0.1 g,preferably 0.01 to 0.05 g, per kilogram of seed are generally necessary.

When used in the protection of materials or stored products, the amountof active compound applied depends on the kind of application area andon the effect desired. Amounts customarily applied in the protection ofmaterials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg,of active compound per cubic meter of treated material.

The compounds I can be converted to the usual formulations, e.g.solutions, emulsions, suspensions, dusts, powders, pastes and granules.The application form depends on the respective use intended; it shouldin any case guarantee a fine and uniform distribution of the compoundaccording to the invention.

The formulations are prepared in a known way, e.g. by extending theactive compound with solvents and/or carriers, if desired usingemulsifiers and dispersants, it being possible, when water is thediluent, also to use other organic solvents as auxiliary solvents.Suitable auxiliaries for this purpose are essentially: solvents, such asaromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes),paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol),ketones (e.g. cyclohexanone), amines (e.g. ethanolamine,dimethylformamide) and water; carriers, such as ground natural minerals(e.g. kaolins, clays, talc, chalk) and ground synthetic ores (e.g.highly dispersed silicic acid, silicates); emulsifiers, such as nonionicand anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates) and dispersants, such aslignosulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid and dibutylnaphthalensulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids, andalkali metal and alkaline earth metal salts thereof, salts of sulfatedfatty alcohol glycol ethers, condensation products of sulfonatednaphthalene and naphthalene derivatives with formaldehyde, condensationproducts of naphthalene or of naphthalenesulfonic acid with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, octylphenol and nonylphenol, alkylphenol polyglycolethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols,isotridecyl alcohol, fatty alcohol ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylatedpolyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitolesters, lignosulfite waste liquors and methylcellulose.

Petroleum fractions having medium to high boiling points, such askerosene or diesel fuel, furthermore coal tar oils, and oils ofvegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons,e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene,alkylated naphthalenes or derivatives thereof, methanol, ethanol,propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol,cyclohexanone, chlorobenzene or isophorone, or highly polar solvents,e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone orwater, are suitable for the preparation of directly sprayable solutions,emulsions, pastes or oil dispersions.

Powders, preparations for broadcasting and dusts can be prepared bymixing or mutually grinding the active substances with a solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active compounds to solidcarriers. Solid carriers are, e.g., mineral earths, such as silica gels,silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers, such as, e.g.,ammonium sulfate, ammonium phosphate, ammonium nitrate or ureas, andplant products, such as cereal meal, tree bark meal, wood meal andnutshell meal, cellulose powders and other solid carriers.

The formulations generally comprise between 0.01 and 95% by weight,preferably between 0.1 and 90% by weight, of the active compound. Theactive compounds are employed therein in a purity of 90% to 100%,preferably 95% to 100% (according to the NMR spectrum).

Examples for formulations are:

I. 5 parts by weight of a compound according to the invention areintimately mixed with 95 parts by weight of finely divided kaolin. Inthis way, a dust comprising 5% by weight of the active compound isobtained.

II. 30 parts by weight of a compound according to the invention areintimately mixed with a mixture of 92 parts by weight of pulverulentsilica gel and 8 parts by weight of liquid paraffin, which had beensprayed onto the surface of this silica gel. In this way, an activecompound preparation with good adhesive properties (active compoundcontent 23% by weight) is obtained.

III. 10 parts by weight of a compound according to the invention aredissolved in a mixture consisting of 90 parts by weight of xylene, 6parts by weight of the addition product of 8 to 10 mol of ethylene oxidewith 1 mol of the N-monbethanolamide of oleic acid, 2 parts by weight ofthe calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight ofthe addition product of 40 mol of ethylene oxide with 1 mol of castoroil (active compound content 9% by weight).

IV. 20 parts by weight of a compound according to the invention aredissolved in a mixture consisting of 60 parts by weight ofcyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight ofthe addition product of 7 mol of ethylene oxide with 1 mol ofisooctylphenol and 5 parts by weight of the addition product of 40 molof ethylene oxide with 1 mol of castor oil (active compound content 16%by weight).

V. 80 parts by weight of a compound according to the invention areintimately mixed with 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodiumsalt of a lignosulfonic acid from a sulfite waste liquor and 7 parts byweight of pulverulent silica gel and are ground in a hammer mill (activecompound content 80% by weight).

VI. 90 parts by weight of a compound according to the invention aremixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solutionis obtained which is suitable for use in the form of very small drops(active compound content 90% by weight).

VII. 20 parts by weight of a compound according to the invention aredissolved in a mixture consisting of 40 parts by weight ofcyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight ofthe addition product of 7 mol of ethylene oxide with 1 mol ofisooctylphenol and 10 parts by weight of the addition product of 40 molof ethylene oxide with 1 mol of castor oil. By running the solution into100 000 parts by weight of water and finely dispersing it therein, anaqueous dispersion is obtained comprising 0.02% by weight of the activecompound.

VIII. 20 parts by weight of a compound according to the invention areintimately mixed with 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodiumsalt of a lignosulfonic acid from a sulfite waste liquor and 60 parts byweight of pulverulent silica gel and are ground in a hammer mill. Aspray emulsion comprising 0.1% by weight of the active compound isobtained by fine dispersion of the mixture in 20 000 parts by weight ofwater.

The active compounds can be used as such, in the form of theirformulations or of the application forms prepared therefrom, e.g. in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dusts, preparations forbroadcasting or granules, by spraying, atomizing, dusting, broadcastingor watering. The application forms depend entirely on the intended uses;they should always guarantee the finest possible dispersion of theactive compounds according to the invention.

Aqueous use forms can be prepared from emulsifiable concentrates, pastesor wettable powders (spray powders, oil dispersions) by addition ofwater. To prepare emulsions, pastes or oil dispersions, the substancescan be homogenized in water, as such or dissolved in an oil or solvent,by means of wetting agents, tackifiers, dispersants or emulsifiers.However, concentrates comprising active substance, wetting agent,tackifier, dispersant or emulsifier and possibly solvent or oil can alsobe prepared, which concentrates are suitable for dilution with water.

The concentrations of active compound in the ready-for-use preparationscan be varied within relatively wide ranges. In general, they arebetween 0.0001 and 10%, preferably between 0.01 and 1%.

The active compounds can also be used with great success in the ultralow volume (ULV) process, it being possible to apply formulations withmore than 95% by weight of active compound or even the active compoundwithout additives.

Oils of various types, herbicides, fungicides, other pesticides andbactericides can be added to the active compounds, if need be too notuntil immediately before use (tank mix). These agents can be added tothe preparations according to the invention in a weight ratio of 1:10 to10:1.

The preparations according to the invention can, in the application formas fungicides, also be present together with other active compounds,e.g. with herbicides, insecticides, growth regulators, fungicides oralso with fertilizers. On mixing the compounds I or the preparationscomprising them in the application form as fungicides with otherfungicides, in many cases an expansion of the fungicidal spectrum ofactivity is obtained.

The following lists of fungicides, with which the compounds according tothe invention can be used in conjunction, is intended to illustrate thepossible combinations but does not limit them:

-   -   acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl,    -   amine derivatives, such as aldimorph, dodine, dodemorph,        fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine        or tridemorph,    -   anilinopyrimidines, such as pyrimethanil, mepanipyrim or        cyprodinil,    -   antibiotics, such as cycloheximide, griseofulvin, kasugamycin,        natamycin, polyoxin or streptomycin,    -   azoles, such as bitertanol, bromoconazole, cyproconazole,        difenoconazole, diniconazole, epoxiconazole, fenbuconazole,        fluquinconazole, flusilazole, flutriafol, hexaconazole,        imazalil, metconazole, myclobutanil, penconazole, propiconazole,        prochloraz, prothioconazole, tebuconazole, triadimefon,        triadimenol, triflumizole or triticonazole,    -   dicarboximides, such as iprodione, myclozolin, procymidone or        vinclozolin,    -   dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam,        metiram, propineb, polycarbamate, thiram, ziram or zineb,    -   heterocyclic compounds, such as anilazine, benomyl, boscalid,        carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet,        dithianon, famoxadone, fenamidone, fenarimol, fuberidazole,        flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol,        probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen,        silthiofam, thiabendazole, thifluzamide, thiophanate-methyl,        tiadinil, tricyclazole or triforine,    -   copper fungicides, such as Bordeaux mixture, copper acetate,        copper oxychloride or basic copper sulfate,    -   nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton        or nitrothal-isopropyl, phenylpyrroles, such as fenpiclonil or        fludioxonil,    -   sulfur,    -   other fungicides, such as acibenzolar-S-methyl, benthiavalicarb,        carpropamid, chlorothalonil, cyflufenamid, cymoxanil, dazomet,        diclomezine, diclocymet, diethofencarb, edifenphos, ethaboxam,        fenhexamid, fentin acetate, fenoxanil, ferimzone, fluazinam,        fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene,        metrafenone, pencycuron, propamocarb, phthalide,        tolclofos-methyl, quintozene or zoxamide,    -   strobilurins, such as azoxystrobin, dimoxystrobin,        fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,        picoxystrobin, pyraclostrobin or trifloxystrobin,    -   sulfenic acid derivatives, such as captafol, captan,        dichlofluanid, folpet or tolylfluanid,    -   cinnamamides and analogous compounds, such as dimethomorph,        flumetover or flumorph.

SYNTHESIS EXAMPLES

The procedure described in the following synthesis example was used toprepare further compounds I by appropriate modification of the startingcompounds. The compounds thus obtained are listed in the followingtable, together with physical data.

Example 1 Preparation of5-chloro-6-(2,4,6-trifluorophenyl)-7-(1-methyl-2-propen-1-yl)amino[1,2,4]triazolo[1,5-a]pyrimidine[I-1]

A solution of 1,5 mmol of (1-methyl-2-propen-1-yl)amine [cf. U.S. Pat.No. 4,120,901; J. Chem. Soc., Chem. Commun., p. 794 (1984)] and 1,5 mmolof triethylamine in 10 ml of dichloromethane was added, with stirring,to a solution of 1.5 mmol of5,7-dichloro-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine[cf. WO 98/46607] in 20 ml of dichloromethane. The reaction mixture wasstirred at 20-25° C. for approximately 16 hours and was then washed withdilute HCl solution. After separation of the phases, the organic phasewas dried and freed from the solvent. After chromatographing the residueon silica gel, 0.52 g of the title compound was obtained, with a meltingpoint of 101° C.

Example 2 Preparation of5-cyano-6-(2,4,6-trifluorophenyl)-7-(2,5-dimethylpyrrod-3-en-1-yl)amino[1,2,4]triazolo[1,5-a]pyrimidine

A mixture of 0.1 mol of the compound 1-10 and 0.25 mol oftetraethylammonium cyanide in 750 ml of dimethylformamide (DMF) wasstirred at 20-25° C. for approximately 16 hours. After addition of waterand methyl tert-butyl ether (MTBE) and phase separation, the organicphase was washed with water, then dried and freed from solvent. Afterchromatographing the residue on silica gel, 4.32 g of the title compoundwere obtained, with a melting point of 206° C.

Example 3 Preparation of5-methoxy-6-(2,4,6-trifluorophenyl)-7-(2,5-dimethylpyrrod-3-en-1-yl)amino[1,2,4]triazolo[1,5-a]pyrimidine

A solution of 65 mmol of the compound 1-10 in 400 ml of anhydrousmethanol was treated with 71.5 mmol of sodium methoxide solution (30%)at 20-25° C. After stirring at this temperature for approximately 16hours, the solvent was distilled off and the residue was taken up indichloromethane. After washing with water, the organic phase was driedand then freed from solvent. After chromatographing the residue onsilica gel, 4.05 g of the title compound were obtained, with a meltingpoint of 149° C.

Example 4 Preparation of5-methyl-6-(2,4,6-trifluorophenyl)-7-(2,5-dimethylpyrrod-3-en-1-yl)amino[1,2,4]triazolo[1,5-a]pyrimidine

A mixture of 20 ml of diethyl malonate and 0.27 g (5.65 mmol) of sodiumhydride (50% dispersion in mineral oil) in 50 ml of acetonitrile wasstirred at 20-25° C. for approximately 2 hours. 4.7 mmol of the compound1-10 were added and then the mixture was stirred at 60° C. forapproximately 20 hours. After addition of 50 ml of aqueous ammoniumchloride solution, acidification was carried out with dilute HClsolution and then the mixture was extracted with MTBE. After drying, thecombined organic phases were freed from the solvent. The crude productwas purified by chromatographing on silica gel and was taken up inconcentrated HCl, and the mixture was then stirred at 80° C. forapproximately 24 hours. After cooling, the pH was adjusted to 5 withaqueous NaOH solution and the reaction mixture was extracted with MTBE.After drying, the combined organic phases were freed from the solvent.After chromatographing the residue on silica gel, 0.62 g of the titlecompound was obtained.

¹H NMR (8 in ppm): 8.42 (s); 6.85 (m); 5.75 (s); 4.75 (q); 2.42 (s);1.10 (s). TABLE I I

No. R¹ R² R³ R⁴ X L_(m) Phys. data (M.p. [° C.]) I-1 CH₃ H CH═CH₂ H Cl2,4,6-F₃ 101 I-2 CH₃ H C(CH₃)═CH₂ H Cl 2,4,6-F₃ 154 I-3 CH₃ H CH═CHCH₃ HCl 2,4,6-F₃ 86 I-4 CH₃ H CH═C(CH₃)₂ H Cl 2,4,6-F₃ 143 I-5 CH₃ HC(CH₃)═CHCH₃ H Cl 2,4,6-F₃ 127 I-6 CH₃ H CH═C(CH₃)₂ H Cl 2-CH₃-4-F 115I-7 CH₃ H C(CH₃)═CHCH₃ H Cl 2-CH₃-4-F 105 I-8 CH₃ H —CH═CHC(CH₃)-# Cl2-Cl-6-F 131 I-9 CH₃ H —CH═CHC(CH₃)-# Cl 2,6-F₂ 143 I-10 CH₃ H—CH═CHC(CH₃)-# Cl 2,4,6-F₃ 105 I-11 CH₃ H CH═C(CH₃)₂ H Cl 2,4-F₂ 118I-12 CH₃ H C(CH₃)═CHCH₃ H Cl 2,4-F₂ 111 I-13 CH₃ H —CH═CHC(CH₃)-# Cl2-Cl 151 I-14 CH₃ H —CH═CHC(CH₃)-# Cl 2-F 149 I-15 CH₃ H CH═CH₂ H Cl2-CH₃-4-F 96 I-16 CH₃ H C(CH₃)═CH₂ H Cl 2-CH₃-4-F 121 I-17 CH₃ HCH═CHCH₃ H Cl 2-CH₃-4-F 85 I-18 CH₃ H CH₂CH═CH₂ H Cl 2,4,6-F₃ 105 I-19CH₃ H CH₂CH═CH₂ H Cl 2-CH₃-4-F 126 I-20 CH₃ H CH═CH₂ H Cl 2,4-F₂ 72 I-21CH₃ H C(CH₃)═CH₂ H Cl 2,4-F₂ 92 I-22 CH₃ H CH═CHCH₃ H Cl 2,4-F₂ 72 I-23CH₃ H CH═CH₂ H Cl 2-Cl-4-F 80 I-24 CH₃ H C(CH₃)═CH₂ H Cl 2-Cl-4-F 72I-25 CH₃ H CH═CHCH₃ H Cl 2-Cl-4-F 98 I-26 CH₃ H CH═C(CH₃)₂ H Cl 2-Cl-4-F132 I-27 CH₃ H CH═CH₂ CH₃ Cl 2,4,6-F₃ 158 I-28 CH₃ H CH═CH₂ CH₂CH₃ Cl2,4,6-F₃ 91 I-29 CH₃ H (CH₂)₂CH═CH₂ H Cl 2,4,6-F₃ 119 I-30 CH₃ H—CH₂CH═CHCH₂-# Cl 2,4,6-F₃ 151 I-31 CH₃ H (CH₂)₂CH═CH₂ H Cl 2-CH₃-4-F107 I-32 CH₃ H —CH═CHC(CH₃)-# Cl 2-CH₃-4-F 183 I-33 CH₃ H C(CH₃)═CHCH₃ HCl 2-CH₃-4-F 118 I-34 CH₃ H (CH₂)₂CH═CH₂ H Cl 2,4-F₂ 90 I-35 CH₃ H(CH₂)₂CH═CH₂ H Cl 2-Cl-4-F 98# indicates the bond to the nitrogen atom

Because of the hindered rotation of the phenyl group, twodiastereoisomers may exist which may differ in their physicalproperties.

Examples for the action against harmful fungi

The fungicidal action of the compounds of the formula I can bedemonstrated by the following tests:

The active compounds were prepared, separately or together, as a stocksolution with 0.25% by weight of active compound in acetone or DMSO. 1%by weight of the emulsi-fier Uniperol® EL (wetting agent with anemulsifying and dispersing action based on ethoxylated alkylphenols) wasadded to this solution and appropriately diluted with water to thedesired concentration.

Use Example 1 Activity Against Early Blight of Tomato Caused byAlternaria solani

Leaves of pot plants of the variety “Grope Fleischtomate St. Pierre”were sprayed to runoff point with an aqueous suspension in the activecompound concentration given below. On the following day, the leaveswere infected with an aqueous suspension of spores of Alternaria solaniin 2% Biomalz solution with a concentration of 0.17×10⁶ spores/ml. Theplants were subsequently placed in a chamber saturated with water vaporat temperatures between 20 and 22° C. After 5 days, leaf infection inthe untreated but infected control plants had so extensively developedthat the infection could be visually determined in %.

In this test, the plants treated with 250 ppm of the active compoundsNos. I-1, I-5 and I-7 showed no infection, while the untreated plantswere 100% infected.

Use Example 2 Activity Against Gray Mold on Capsicum Leaves Caused byBotrytis cinerea

Capsicum seedlings of the variety “Neusiedler Ideal Elite” were, after4-5 leaves had fully developed, sprayed to runoff point with an aqueoussuspension in the active compound concentration given below. The nextday, the treated plants were inoculated with a spore suspension ofBotrytis cinerea comprising 1.7×10⁶ spores/ml in a 2% aqueous Biomalzsolution. The test plants were subsequently placed in acontrolled-environment chamber at 22 to 24° C. and high atmospherichumidity. After 5 days, the extent of fungal infection on the leavescould be determined visually in %.

In this test, the plants treated with 250 ppm of the active compoundsNos. I-1, I-5 and I-7 showed up to 3% infection, while the untreatedplants were 80% infected.

1. A method for the control of harmful phytopathogenic fungi, whichcomprises treating the fungi or the materials, plants, ground or seedsto be protected from fungal attach with an effective amount of acompound of the formula I

in which the substituents have the following meanings: L is,independently of one another, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆alkoxy, amino, NHR, or NR₂, R is C₁-C₈-alkyl or C₁-C₈alkylcarbonyl;m is 1, 2, 3, 4, or 5 X is halogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkylor C₁-C₄-alkoxy; R¹ is C₁-C₃-alkyl or c₁-C₃-haloalkyl; R² is hydrogen,C₁-C₃-alkyl or C₁-C₃-haloalkyl; R³ is C₂-C₁₀-alkenyl, which can beunsubstituted or partially or completely halogenated or can carry one tothree R^(a) groups: R^(a) is halogen, cyano, nitro, hydroxyl,C₁-C₆-alkylcarbonyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylthio, C₁-C₆-alkylamino,di(C₁-C₆-alkyl)amino, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, C₃-C₆-alkynyloxyor C₃-C₆-cycloalkyl, these aliphatic or alicyclic groups for their partbeing able to be partially or completely halogenated or to carry one tothree R^(b) groups: R^(b) is halogen, cyano, nitro, hydroxyl, mercapto,amino, carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl,alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio,alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl,alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl,di-alkylaminocarbonyl, alkylaminothiocarbonyl ordialkylaminothiocarbonyl, the alkyl groups in these radicals comprising1 to 6 carbon atoms and the abovementioned alkenyl or alkynyl groups inthese radicals comprising 2 to 8 carbon atoms; R⁴ is hydrogen orC₁-C₂-alkyl, R³ and R⁴ can also, together with the nitrogen atom towhich they are bonded, form a five- or six-membered unsaturated ringwhich can carry one or more R^(a) substituents.
 2. The7-(alkenylamino)triazolopyrimidine of the formula I according to claim1, with the exclusion of compounds in which the ring formed by R³ and R⁴together is a dihydropyrrole.
 3. The compound of the formula I accordingto claim 1, in which R³ is C₂-C₁₀-alkenyl, which can be unsubstituted orpartially or completely halogenated or can carry one to three R^(a)groups: R^(a) is halogen, cyano, nitro, hydroxyl, C₁-C₆-alkylcarbonyl,C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkoxycarbonyl,C₁-C₆-alkylthio, C₁-C₆-alkylamino, di(C₁-C₆-alkyl)amino, C₂-C₆-alkenyl,C₂-C₆-alkenyloxy, C₃-C₆-alkynyloxy or C₃-C₆-cycloalkyl, these aliphaticor alicyclic groups for their part being able to be partially orcompletely halogenated or to carry one to three R^(b) groups: R^(b) ishalogen, cyano, nitro, hydroxyl, mercapto, amino, carboxyl,aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy,alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino,formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl,alkylcarbonyloxy, alkylaminocarbonyl, di-alkylaminocarbonyl,alkylaminothiocarbonyl or dialkylaminothiocarbonyl, the alkyl groups inthese radicals comprising 1 to 6 carbon atoms and the abovementionedalkenyl or alkynyl groups in these radicals comprising 2 to 8 carbonatoms; R⁴ is hydrogen or C₁-C₂-alkyl.
 4. The compound of the formula Iaccording to claim 2, wherein X represents chlorine or methyl, inparticular chlorine.
 5. The compound of the formula I according to claim2, wherein R¹ represents methyl or halomethyl.
 6. The compound of theformula I according to any of claims 2 to 5 claim 2, wherein R²represents hydrogen.
 7. The compound of the formula I according to anyof claims 2 to 6 claim 2, wherein the phenyl group substituted by L_(m)is the group A

in which # is the point of linkage with the triazolopyrimidine skeletonand L¹ represents fluorine, chlorine, CH₃ or CF₃; L² and L⁴ represent,independently of one another, hydrogen or fluorine; L³ representshydrogen, fluorine, chlorine, CH₃, OCH₃, amino, NHR or NR²; and L⁵represents hydrogen, fluorine or CH₃.
 8. The compound of the formula Iaccording to claim 2, wherein the phenyl group substituted by L_(m) isone of the following substituent combinations: 2-fluoro-6-chloro,2,6-difluoro, 2,6-dichloro, 2-fluoro-6-methyl, 2,4,6-trifluoro,2,6-difluoro-4-methoxy, pentafluoro, 2-methyl-4-fluoro,2-trifluoromethyl, 2-methoxy-6-fluoro, 2-chloro, 2-fluoro, 2,4-difluoro,2-fluoro-4-chloro, 2-chloro-4-fluoro, 2,3-difluoro, 2,5-difluoro,2,3,4-trifluoro, 2-methyl, 2,4-dimethyl, 2-methyl-4-chloro,2-fluoro-4-methyl, 2,6dimethyl, 2,4,6-trimethyl, 2,6-difluoro-4-methyl,2-trifluoromethyl-4-fluoro, 2-trifluoromethyl-5-fluoro or2-trifluoromethyl-5-chloro.
 9. A process for the preparation of thecompound of the formula I according to claim 2 by reaction ofdihalotriazolopyrimidines of the formula II,

in which the variables have the meaning given for formula I and Hal is ahalogen atom, in particular chlorine, with amines of the formula III.


10. A composition suitable for the control of harmful fungi, comprisinga solid or liquid carrier and a compound of the formula I according toclaim 1.